JP2018035355A - Monomers, polymers, and photoresist compositions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide new photoresist compositions that may provide enhanced imaging capabilities.SOLUTION: The invention provides polymers comprising a structure represented by the formula (I), and photoresists that comprises the polymers. (X and X' are each independently a linker; R is H or a non-hydrogen substituent; A and B are each independently H or F; R' and R" are each independently H or a non-hydrogen substituent, with at least one of R' and R" being a non-hydrogen substituent other than a halogen or a halogen-substituted group when R is hydrogen.)SELECTED DRAWING: None

Description

  The present invention relates generally to the manufacture of electronic devices. More specifically, the present invention relates to photoresist compositions and photolithography processes that allow the formation of fine patterns using a negative tone development process.

  A photoresist is a photosensitive film used for transfer of an image to a substrate. A coating layer of photoresist is formed on the substrate, and the photoresist layer is then exposed to an activating radiation source through a photomask. After exposure, the photoresist is developed to provide a relief image that allows selective processing of the substrate.

  Considerable efforts have been made to extend the practical resolution capability of photoresist compositions, including through immersion lithography. In immersion lithography, the numerical aperture of the exposure tool lens increases through the use of fluid to focus more light onto the resist film. More specifically, immersion lithography utilizes a relatively high refractive index fluid between the last surface of an imaging device (eg, ArF stepper) and the first surface on a wafer or other substrate. US 2012 / 0171626A1, US 7,968,268B2, US 2011 / 0255069A1, Korea KR11412229B1, KR200006014393A1, KR2009028739A1, KR200909046730A1, and Korea 7 I want to be.

  Electronic device manufacturers are constantly seeking increased resolution of patterned photoresist images. It would be desirable to have new photoresist compositions that can provide enhanced imaging capabilities.

  We now provide new polymers and photoresists containing such polymers.

  In one preferred embodiment, there is provided a polymer comprising the structure of formula (I):

In formula (I),
X and X ′ are the same or different linkers;
R is hydrogen or a non-hydrogen substituent,
A and B are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent;
At least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen.

  In a further embodiment, a polymer comprising the structure of the following formula (IIA) is provided:

In formula (IIA),
X and X ′ are the same or different linkers;
R is hydrogen or a non-hydrogen substituent,
A and B are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent;
At least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen.

In certain preferred polymers of formula (I) or (IIA), R ′ and R ″ are each independently hydrogen, non-halogenated alkyl, or heteroalkyl. In certain additional preferred polymers of formula (I) or (IIA), X and X ′ may be different, or in other preferred polymers, X and X ′ may be the same. In various preferred polymers of formula (I) or (IIA), at least one or both of X and X ′ is a chemical bond or —CH ₂ —.

  In yet a further embodiment, a polymer comprising the structure of formula (IIB) below is provided:

In formula (IIB),
X, X ′, and X ″ are each the same or different linkers;
A ′, B ′, and C ′ are each independently hydrogen or fluorine,
R ′, R ″, and R ′ ″ are each independently hydrogen or a non-hydrogen substituent.

In certain preferred polymers of formula (IIB), R ′, R ″, and R ′ ″ are each independently hydrogen, non-halogenated alkyl, or heteroalkyl. In certain additional preferred polymers of formula (IIB), at least two of X, X ′, and X ″ are different, or in other preferred polymers, at least two of XX ′ and X ″. May be the same. In various preferred polymers of formula (IIB), at least one, two, or each of XX ′ and X ″ is a chemical bond or —CH ₂ —.

  The polymer of the present invention may comprise a plurality of different repeating units. Thus, the polymer may be a homopolymer, more typically a copolymer, terpolymer, tetrapolymer, pentapolymer, or other having 2, 3, 4, 5, or more different repeat units. Higher order polymers. Such additional repeat units need not comprise the structure of formula (I), (IIA), or (IIB) above, provided that at least one unit of the polymer is of formula (I), (IIA) above. ) Or (IIB).

  Particularly preferred polymers of the present invention may contain polymerized acrylate units. In related embodiments, preferred polymers include those in which the polymer comprises units obtained by polymerization of one or more monomers of the following formula (III):

In formula (III),
Y is hydrogen or optionally substituted alkyl;
X and X ′ are the same or different linkers;
R is hydrogen or a non-hydrogen substituent,
A ′, B ′, and C ′ are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent;
At least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen. In formula (III), Y is suitably hydrogen, or optionally substituted C _1-3 alkyl, including optionally substituted methyl. In certain preferred polymers of formula (IIB), R ′, R ″, and R ′ ″ are each independently hydrogen, non-halogenated alkyl, or heteroalkyl. In certain additional preferred polymers of formula (IIB), at least two of X, X ′, and X ″ are different, or in other preferred polymers, at least two of XX ′ and X ″. May be the same. In various preferred polymers of formula (IIB), at least one, two, or each of XX ′ and X ″ is a chemical bond or —CH ₂ —.

  Preferred polymers are those in which at least one or both of A and B are fluorine (formulas I, IIA, IIB, III) or at least one, two of A ′, B ′, and C ′ Or each is fluorine (including polymers of formula (IIB)).

  One or more disclosed herein comprising one or more acid generators and a polymer comprising a structure of any of formulas (I), (IIA), or (IIB) disclosed above. And a polymer. In a preferred embodiment, the photoresist of the present invention may comprise a second polymer that is different from any polymer of formula (I), (IIA) or (IIB). The polymer comprising the structure of any one of formulas (I), (IIA) or (IIB) is in part referred to herein as the “first polymer” of the photoresist composition. In certain preferred embodiments, the photoresist may comprise an additional polymer that is different from the first polymer (sometimes referred to herein as the “second polymer” of the photoresist composition). . The second polymer may optionally contain acid labile groups. As will be discussed further below, in certain embodiments, the first and second polymers may have different surface energies.

  In certain preferred embodiments, the first polymer is a repeating unit comprising (1) one or more hydrophobic groups and (2) a structure of formula (I), (IIA) or (IIB). A third unit may be further included. Preferably, such one or more hydrophobic groups each comprise 3, 4, 5, 6, 7, 8 or more carbon atoms.

  Also provided is a method of processing a photoresist composition, applying a layer of the photoresist composition disclosed herein on a substrate, exposing the photoresist composition layer to activating radiation, And developing the exposed photoresist composition to provide a photoresist relief image. Suitably, the photoresist composition layer may be immersion exposed. Dry (non-immersion) exposure is also suitable. In certain aspects, implants and EUV lithography processes are also preferred.

  In a preferred embodiment, the unexposed portions of the photoresist layer are removed by the developer, leaving the photoresist pattern across one or more layers to be patterned. Patterned exposure can be performed by immersion lithography or using dry exposure techniques.

  According to a further aspect, a coated substrate is provided. The coated substrate includes a substrate and a layer of the photoresist composition of the present invention over the surface of the substrate.

  Also provided are electronic devices formed by the disclosed methods, including devices formed by the disclosed negative tone development process.

  Monomers comprising the structure of any one of formulas (I), (IIA), (IIB) or (III) disclosed above are also provided.

  As used herein, the articles “a” and “an” include one or more unless explicitly or by context.

  Other aspects of the invention are disclosed below.

  As discussed, in certain preferred embodiments, the photoresist of the present invention comprises at least two different polymers, 1) a first polymer comprising a structure of formula (I), (IIA), or (IIB) and 2) A second polymer different from the first polymer may be included. The second polymer need not include the structure of formula (I), (IIA), or (IIB). In preferred compositions, the first polymer can move toward the top surface of the resist coating layer during coating of the photoresist composition. In certain systems, this can form a surface layer substantially composed of the first polymer. Following exposure and post-exposure bake (PEB), the resist coating layer can be developed, including in a developer containing an organic solvent. When organic developers are employed, such developers remove the unexposed areas of the photoresist layer and the surface layer of the exposed areas. An aqueous alkaline developer that removes the exposed areas of the resist coating layer may also be utilized. The advantages of the photoresist composition of the present invention can be achieved when using the composition in a dry or immersion lithography process. When used in immersion lithography, preferred photoresist compositions can further exhibit reduced migration (leaching) of the photoresist material into the immersion liquid, which is also the result of movement of the addition polymer to the resist surface. . Significantly, this can be achieved without the use of a topcoat layer over the photoresist.

  Photoresists can be used at various emission wavelengths, eg, sub-400 nm, sub-300 or 200 nm, or exposure wavelengths of 248 nm, 193 nm, and EUV (eg, 13.5 nm) are preferred. The composition may further be used in an electron beam (E beam) exposure process. The photoresist composition of the present invention is preferably a chemically amplified material.

  As discussed, the first polymer or addition polymer useful in the photoresist composition comprises a structure of formula (I), (IIA), or (IIB) above. Such polymers may be prepared by polymerization of one or more monomers of the following structure:

In each of the above formulas (A), (B), (C), (D), (E), and (F), each R ₁ is independently halogen-substituted C _3-16 alkyl, especially fluoro-substituted An optionally substituted alkyl, including C _3-16 alkyl, such as C _1-20 alkyl, more typically a non-hydrogen substituent such as C _3-16 alkyl, where R ₂ is an unsubstituted C _1- Non-hydrogen substitution, such as optionally substituted alkyl, including ₁₂ alkyl, especially unsubstituted alkyl having 1, 2, 3, 4, or 5 carbon atoms.

  Exemplary preferred monomers of formula (A) above include:

  Exemplary preferred monomers of formula (B) above include:

  Exemplary preferred monomers of formula (D) above include:

  Compounds of formula (A), (B), (C), (D), (E), and (F) above can be readily prepared. For example, polyhydroxy acrylate or methacrylate compounds can be acylated under basic conditions. The polyhydroxy acrylate or methacrylate compound can be reacted with an optionally substituted alkyl carboxy compound, including halogenated, especially fluorinated alkyl carboxy compounds. See, for example, Examples 1-6 below.

  Polymers containing structures of formula (I), (IIA), or (IIB) can also be readily prepared. For example, the polymerizable compounds of the above formulas (A), (B), (C), (D), (E), and (F) can be reacted to provide a homopolymer, or Reacted with other different compounds, copolymer (at least 2 different repeat units), terpolymer (3 different repeat units), tetrapolymer (4 different repeat units), or pentapolymer (5 different repeat units) Higher order polymers such as can be provided. See Examples 7-12 below for exemplary preferred syntheses.

Optional second polymer of photoresist In a preferred embodiment, the photoresist composition comprises one or more second polymers or matrix polymers (different from the first polymer) comprising acid labile groups. An acid labile group is a chemical moiety that readily undergoes a deprotection reaction in the presence of an acid. The second polymer or matrix polymer as part of the layer of photoresist composition may generate photoacid and / or thermal acid during lithographic processing, especially after soft baking, exposure to activating radiation, and post exposure baking. As a result of the reaction with the acid generated from the agent, it undergoes a change in solubility in the developer described herein. This is due to photoacid-induced cleavage of the acid labile group, causing a change in the polarity of the second polymer. The acid labile group can be selected from, for example, tertiary alkyl carbonates, tertiary alkyl esters, tertiary alkyl ethers, acetals, and ketals. Preferably, the acid labile group is an ester group containing a tertiary acyclic alkyl carbon or tertiary alicyclic carbon covalently bonded to the carboxyl oxygen of the ester of the second matrix polymer. Such cleavage of acid labile groups results in the formation of carboxylic acid groups. Suitable units containing acid labile groups include, for example, t-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-isopropylcyclopentyl (meth) acrylate, 1-propylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-isopropylcyclohexyl (meth) acrylate, 1-propylcyclohexyl (meth) acrylate , T-butylmethyladamantyl (meth) acrylate, acid labile (alkyl) acrylate units such as ethylphenkyl (meth) acrylate, and other cyclics including alicyclic and acyclic (alkyl) acrylates It is. Acetal and ketal acid labile groups can be substituted in place of hydrogen atoms at the end of alkali-soluble groups such as carboxyl groups or hydroxyl groups in order to be bonded to oxygen atoms. When the acid is generated, the acid cleaves the bond between the acetal or ketal group and the oxygen atom to which the acetal-type dissociable, dissolution inhibiting group is bound. Exemplary such acid labile groups are, for example, US Pat. No. 6,057,083, US Pat. No. 6,136,501, and US Pat. No. 8,206,886, and European Patent Publication No. EP01008913A1. And EP 00930542 A1. Acetal and ketal groups as part of the sugar derivative structure are also suitable, and their cleavage results in the formation of hydroxyl groups as described, for example, in US Patent Application US2012 / 0064456A1.

  For imaging at certain sub-200 nm wavelengths, such as 193 nm, the second polymer or matrix polymer is typically a phenyl, benzyl, or other aromatic group (such groups are highly radiant. (Absorbing) is substantially free (for example, less than 15 mol%), preferably completely free. Suitable polymers that are substantially or completely free of aromatic groups are disclosed in European Patent Publication No. EP930542A1 and US Pat. Nos. 6,692,888 and 6,680,159.

  Other suitable second polymers or matrix polymers include, for example, polymers containing polymerized units of non-aromatic cyclic olefins (intracyclic double bonds) such as optionally substituted norbornene, such as US Pat. , 843,624 and 6,048,664. Still other suitable matrix polymers include polymerized anhydride units, particularly polymerized maleic anhydride and / or itaconic acid, such as those disclosed in European published application EP01008913A1 and US Pat. No. 6,048,662. Examples include polymers containing anhydride units.

  Resins containing repeating units containing heteroatoms, especially oxygen and / or sulfur (but other than anhydrides, ie, these units do not contain keto ring atoms) are also suitable as the second polymer or matrix polymer. It is. Heteroalicyclic units can be condensed to the polymer backbone, such as those provided by polymerization of norbornene groups and / or anhydride units, such as provided by polymerization of maleic anhydride or itaconic anhydride. Cyclic units can be included. Such polymers are disclosed in International Publication No. WO 01/86353 A1 and US Pat. No. 6,306,554. Other suitable heteroatom group containing matrix polymers include one or more heteroatom (eg, oxygen or sulfur) containing groups, such as hydroxy, as disclosed in US Pat. No. 7,244,542. And polymers containing polymerized carbocyclic aryl units substituted with a naphthyl group.

  For sub-200 nm wavelengths such as 193 nm and EUV (eg, 13.5 nm), the second polymer or matrix polymer contains a lactone moiety to control the dissolution rate of the second matrix polymer and the photoresist composition. The unit to be included may be included. Suitable monomers for use in the second polymer or matrix polymer containing a lactone moiety include, for example:

  Such second polymer or matrix polymer typically provides additional means to enhance the etch resistance of the matrix polymer and photoresist composition and to control the dissolution rate of the matrix polymer and photoresist composition. Further comprising a unit containing a polar group. Monomers for forming such units include, for example:

  The second polymer or matrix polymer can include one or more additional units of the type described above. Typically, the additional units for the second polymer or matrix polymer are the same or similar polymerizable groups used for the monomers used to form the other units of the polymer. But may contain other different polymerizable groups in the same polymer backbone.

  In a preferred embodiment, the second polymer or matrix polymer has a surface energy that is higher than the surface energy of the first polymer or addition polymer described below and is substantially immiscible with the second polymer. Should. As a result of the difference in surface energy, the separation of the second polymer from the first polymer can take place during spin coating. Suitable surface energy of the second polymer or matrix polymer is typically 20-50 mN / m, preferably 30-40 mN / m.

  Without being limited thereto, exemplary second polymers or matrix polymers include, for example:

Second polymers or matrix polymers suitable for use in the photoresist compositions of the present invention are commercially available and can be readily made by those skilled in the art. The second polymer is present in the resist composition in an amount sufficient to render the exposed coating layer of the resist developable in a suitable developer. Typically, the second polymer is present in the composition in an amount of 50-95% by weight based on the total solids of the resist composition. The weight average molecular weight _Mw of the second polymer is typically less than 100,000, such as 3000-100,000, more typically 3000-15,000. A blend of two or more of the second polymers described above can be suitably used in the photoresist composition of the present invention.

The first polymer comprising the structure of formula (I), (IIA), or (IIB) preferably has a surface energy that is lower than the surface energy of the second polymer, preferably with the second polymer A material that is substantially immiscible. In this way, separation or migration of the first polymer to the top or top portion of the applied photoresist layer during the coating process is facilitated. While the desired surface energy of the first polymer is determined by the particular second polymer and its surface energy, the surface energy of the first polymer is typically 18-40 mN / m, preferably 20-35 mN / m m, and more preferably 29 to 33 mN / m. The first polymer moves to the top surface of the resist layer during the coating process, but it is preferred that there is some mixing between the first polymer and the second polymer or matrix polymer just below the resist layer surface. . Such mixing is believed to help reduce surface inhibition in the resist layer by reducing or eliminating acid generated in the dark region near the second polymer or matrix polymer due to stray light. The degree of mixing is determined, for example, by the difference in surface energy (SE) between the second polymer or matrix polymer (MP) and the first polymer or addition polymer (AP) (ΔSE = SE _MP −SE _AP ). . For a given first polymer or matrix polymer and second polymer or addition polymer, the degree of mixing can increase with a decrease in ΔSE. ΔSE is typically 2 to 32 mN / m, preferably 5 to 15 mN / m.

  The first polymer comprising the structure of formula (I), (IIA) or (IIB) is preferably free of silicon. Silicon-containing polymers exhibit significantly lower etch rates than organic photoresist polymers in certain etchants. As a result, agglomeration of the silicon-containing first polymer at the surface of the organic second polymer-based resist layer can cause cone defects during the etching process. The first polymer may contain fluorine or may not contain fluorine. Preferred first polymers are soluble in the same organic solvent (s) used to formulate the photoresist composition. Preferred first polymers are also or become soluble after post-exposure bake (eg, 120 ° C. for 60 seconds) in organic developers used in negative tone development processes.

  As discussed, suitable first polymers comprising a structure of formula (I), (IIA), or (IIB) are as formed from monomers corresponding to the following general formula (I-1) May contain one or more additional different units,

Wherein R ₂ is selected from hydrogen, fluorine, and fluorinated and non-fluorinated C ₁ -C 3 alkyl, X is oxygen or sulfur, R ₄ is substituted and unsubstituted C 1 -C 20 straight chain, From branched and cyclic hydrocarbons, preferably fluorinated and non-fluorinated C1-C15 alkyl, more preferably fluorinated and non-fluorinated C3-C8 alkyl, and most preferably fluorinated and non-fluorinated C4-C5 alkyl. R ₄ is preferably branched to provide a higher water receding contact angle when used in immersion lithography, and R ₄ of haloalkyl and haloalcohols such as fluoroalkyl and fluoroalcohols. Substitution is preferred.

As discussed, various portions of monomers, polymers, and other materials may be optionally substituted (or described as being “substituted or unsubstituted”). “Substituted” substituents include, for example, halogen (especially F, Cl, or Br), cyano, nitro, C _1-8 alkyl, C _1-8 alkoxy, C _1-8 alkylthio, C _1-8 alkylsulfonyl , Alkanoyl such as C _2-8 alkenyl, C _2-8 alkynyl, hydroxyl, nitro, C _1-6 alkanoyl, for example acyl, haloalkyl, in particular C _1-8 haloalkyl, for example CF ₃ , —CONHR, —CONRR ′ (R and R ′ are optionally substituted C _1-8 alkyl), one or more available positions by one or more suitable groups such as —COOH, COC,> C═O, Typically, it may be substituted at 1, 2, or 3 positions.

Exemplary suitable monomers of formula (I-1) are described below, but are not limited to these structures. For purposes of these structures, “R ₂ ” and “X” are as defined above for Formula I-1.

  The photoresist composition preferably comprises a single first polymer comprising a structure of formula (I), (IIA), or (IIB), optionally with one or more additional first polymers Can be included.

  The first polymer comprising the structure of formula (I), (IIA), or (IIB) is typically in a relatively small amount based on the total solids of the photoresist composition, for example, 0.1-0.1 It is present in the photoresist composition in an amount of 10 wt%, preferably 0.5-5 wt%, more preferably 1-3 wt%. The content of the first polymer or addition polymer is, for example, the content of the acid generator in the photoresist layer, the content of the nitrogen-containing group in the first polymer, and the lithography is a dry or immersion type process. It depends on whether or not. For example, the low limit of additional polymers for immersion lithography is generally determined by the need to prevent leaching of resist components. An excessively high first polymer content typically results in pattern degradation. The weight average molecular weight of the addition polymer is typically less than 400,000, preferably 3000 to 50,000, more preferably 3000 to 25,000. Suitable first polymers and monomers for making the first polymers for use in the photoresist compositions of the present invention are commercially available and / or can be made by one skilled in the art.

  The photosensitive composition is preferably one or more photoacid generators (PAGs) employed in an amount sufficient to produce a latent image in the coating layer of the photoresist composition after exposure to activating radiation. ) May be included. For example, the photoacid generator is suitably present in an amount of about 1-20% by weight, based on the total solids of the photoresist composition. Typically, smaller amounts of photoactive components are suitable for chemically amplified resists.

  Suitable PAGs are known in the art of chemically amplified photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (p-tert). -Butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonate esters such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoro) Tansulfonyloxy) benzene, and 1,2,3-tris (p-toluenesulfonyloxy) benzene; diazomethane derivatives such as bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane; glyoxime derivatives such as bis -O- (p-toluene nsulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds such as N- Hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds such as 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, and 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine. One or more of such PAGs can be used.

  Suitable solvents for the photoresist composition of the present invention include, for example, glycol ethers such as 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; methyl lactate and ethyl Lactate such as lactate; propionate such as methyl propionate, ethyl propionate, ethyl ethoxypropionate, and methyl-2-hydroxyisobutyrate; cellosolve ester such as methyl cellosolve acetate; aromatic carbonization such as toluene and xylene Hydrogen; and ketones such as methyl ethyl ketone, cyclohexanone, and 2-heptanone. Blends of solvents such as blends of two, three or more of the above solvents are also suitable. The solvent is typically present in the composition in an amount of 90-99 wt%, more typically 95-98 wt%, based on the total weight of the photoresist composition.

  Other optional additives for the photoresist composition include, for example, actinic and contrast dyes, anti-striation agents, plasticizers, accelerators, sensitizers, and the like. Such optional additives, when used, are typically present in the composition in minor amounts, such as 0.1 to 10% by weight, based on the total solids of the photoresist composition, but may be filled. Agents and dyes can be present at relatively high concentrations, for example, 5-30% by weight based on the total solids of the photoresist composition.

  A preferred optional additive of the resist composition of the present invention is an added base capable of enhancing the resolution of the developed resist relief image. Suitable basic quenchers include, for example, N, N-bis (2-hydroxyethyl) pivalamide, N, N-diethylacetamide, N1, N1, N3, N3-tetrabutylmalonamide, 1-methylazepan-2- Linear and cyclic amides and derivatives thereof such as ON, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2- (hydroxymethyl) propan-2-ylcarbamate; pyridine and di-tert-butyl Aromatic amines such as pyridine; triisopropanolamine, n-tert-butyldiethanolamine, tris (2-acetoxy-ethyl) amine, 2,2 ′, 2 ″, 2 ′ ″-(ethane-1,2-diylbis) (Azantriyl)) tetraethanol, and 2- (dibutylamino) ethanol, , 2 ′, 2 ″ -nitrilotriethanol; 1- (tert-butoxycarbonyl) -4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole Cycloaliphatic amines such as 1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N (2-acetoxy-ethyl) morpholine. Of these basic quenchers, 1- (tert-butoxycarbonyl) -4-hydroxypiperidine and triisopropanolamine are preferred. The added base is suitably used in relatively small amounts, for example 1 to 20% by weight relative to the PAG, more typically 5 to 15% by weight relative to the PAG.

  The photoresist used in accordance with the present invention is generally prepared according to known procedures. For example, the resists of the present invention are suitable solvents such as 2-methoxyethyl ether (diglyme), glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; ethyl lactate or methyl lactate, etc. Lactate (preferably ethyl lactate); propionate, in particular methyl propionate, ethyl propionate, and ethyl ethoxypropionate; cellosolve ester such as methyl cellosolve acetate; aromatic hydrocarbon such as toluene or xylene; or methylethyl By dissolving a photoresist component in one or more of ketones such as, ketone, cyclohexanone, and 2-heptanone. It may be prepared as a coating composition. The desired total solids of the photoresist depends on factors such as the particular polymer in the composition, the final layer thickness, and the exposure wavelength. Typically, the solids content of the photoresist varies from 1 to 10 wt%, more typically 2 to 5 wt%, based on the total weight of the photoresist composition.

  The present invention further provides a method for forming a photoresist relief image and fabricating an electronic device using the photoresist of the present invention. The present invention also provides a novel article of manufacture comprising a substrate coated with the photoresist composition of the present invention.

  In a lithographic process, the photoresist composition can be applied on a variety of substrates. The substrate can include materials such as semiconductors such as silicon or compound semiconductors (eg, III-V or II-VI), glass, quartz, ceramic, copper, and the like. Typically, the substrate is a semiconductor wafer, such as a single crystal silicon or compound semiconductor wafer, and may have one or more layers and patterned features formed on the surface thereof. One or more layers to be patterned may be provided across the substrate. Optionally, for example, when it is desired to form grooves in the substrate material, the underlying bottom substrate material itself may be patterned. When patterning the bottom substrate material itself, the pattern should be considered to be formed in a layer of the substrate.

  The layer may be, for example, one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides or silicides of such metals, layers of doped amorphous silicon or doped polysilicon, One or more dielectric layers such as silicon oxide, silicon nitride, silicon oxynitride, or metal oxide layers, semiconductor layers such as single crystal silicon, and combinations thereof may be included. The layer to be etched can be formed by various techniques such as plasma enhanced CVD, low pressure CVD, or chemical vapor deposition (CVD) such as epitaxial growth, physical vapor deposition (PVD) such as sputtering or evaporation, or electroplating. The particular thickness of the one or more layers 102 that are etched varies depending on the material and the particular device being formed.

  Depending on the particular layer to be etched, the film thickness used and the photolithographic material and process, a hard mask layer and / or bottom antireflective coating (BARC) to be coated with the photoresist layer is placed over the layer May be desirable. For example, the use of a hard mask layer with a very thin resist layer is desirable if the layer to be etched requires significant etch depth and / or if the particular etchant has insufficient resist selectivity possible. When a hard mask layer is used, the formed resist pattern can be transferred to the hard mask layer, which can be used as a mask for etching the sublayer. Suitable hard mask materials and formation methods are known in the art. Typical materials include, for example, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, amorphous carbon, silicon oxynitride, and silicon nitride. The hard mask layer can include a single layer or multiple layers of different materials. The hard mask layer can be formed, for example, by chemical or physical vapor deposition techniques.

  A bottom anti-reflective coating may be desirable if the substrate and / or sublayer reflects a significant amount of incident radiation during photoresist exposure that would otherwise adversely affect the quality of the formed pattern. . Such a coating can improve depth of focus, exposure latitude, line width uniformity, and CD control. Anti-reflective coatings are typically used when the resist is exposed to deep ultraviolet light (300 nm or less), for example, KrF excimer laser light (248 nm), or ArF excimer laser light (193 nm). The antireflective coating can comprise a single layer or multiple different layers. Suitable antireflective materials and methods of formation are known in the art. Anti-reflective materials are commercially available and sold under the AR (TM) trademark by Rohm and Haas Electronic Materials LLC (Marlborough, MA USA) such as AR (TM) 40A and AR (TM) 124 anti-reflective materials. There is something that is.

  A photoresist layer formed from the composition of the present invention described above is applied onto the substrate. The photoresist composition is typically applied to the substrate by spin coating. During spin coating, in resist compositions comprising both the first and second polymers disclosed herein, the first polymer in the photoresist separates onto the top surface of the formed resist layer and is typically Is mixed with the second polymer in the region immediately below the top surface. The solids content of the coating solution can be adjusted to provide the desired film thickness based on the particular coating equipment utilized, the viscosity of the solution, the speed of the coating tool, and the time allowed for spinning. A typical thickness for the photoresist layer is about 500-3000 mm.

  The photoresist layer can then be soft baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving the adhesion of the layer to the substrate. Soft baking can be performed on a hot plate or in an oven, with a hot plate being typical. The soft bake temperature and time are determined, for example, by the specific material and thickness of the photoresist. A typical soft bake is performed at a temperature of about 90-150 ° C. and a time of about 30-90 seconds.

The photoresist layer is then preferably exposed to activating radiation through a photomask, resulting in a solubility difference between the exposed and unexposed areas. In this specification, reference to exposing a photoresist composition to radiation that is activating to the composition indicates that the radiation is capable of forming a latent image in the photoresist composition. . The photomask has optionally transparent areas and optionally opaque areas, corresponding to the areas of the resist layer that remain and are removed respectively in subsequent development steps. The exposure wavelength is typically sub-400 nm, sub-300 nm, or sub-200 nm, with 248 nm, 193 nm, and EUV wavelengths being typical. Photoresist materials can also be used with electron beam exposure. The method finds application in immersion or dry (non-immersion) lithography techniques. The exposure energy is typically about 10-80 mJ / cm ² depending on the exposure tool and the components of the photosensitive composition.

  Following exposure of the photoresist layer, a post-exposure bake (PEB) is performed. PEB can be performed, for example, on a hot plate or in an oven. The conditions for PEB depend on, for example, the particular photoresist composition and layer thickness. PEB is typically performed at a temperature of about 80-150 ° C. and a time of about 30-90 seconds. The latent image defined by the boundary between the polarity-switched area and the non-polar-switched area (corresponding to the exposed and unexposed areas, respectively) is Formed with. The basic portion of the first polymer (eg amine) deprotected during post-exposure bake prevents polarity switching in the dark region of the photoresist layer where stray or scattered light may be present, It is thought to result in a latent image having. This is a result of neutralization of the acid produced by the PAG in the dark region. As a result, cleavage of acid labile groups in those regions can be substantially prevented.

  The exposed photoresist layer is then preferably developed to remove unexposed areas of the photoresist layer. An aqueous alkaline developer such as an alkyl ammonium aqueous developer may be employed. The developer may also be a solvent selected from organic developers, such as ketones, esters, ethers, hydrocarbons, and mixtures thereof. Suitable ketone solvents include, for example, acetone, 2-hexanone, 5-methyl-2-hexanone, 2-heptanone, 4-heptanone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, diisobutylketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, and methyl isobutyl ketone. Suitable ester solvents include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl- Examples include 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate It is done. Suitable ether solvents include, for example, dioxane, tetrahydrofuran, and glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol mono Examples include ethyl ether and methoxymethylbutanol. Suitable amide solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide. Suitable hydrocarbon solvents include, for example, aromatic hydrocarbon solvents such as toluene and xylene. In addition, mixtures of these solvents, or one or more of the listed solvents mixed with solvents other than those mentioned above or mixed with water may be used. Other suitable solvents include those used in the photoresist composition. The developer is preferably butyl acetate such as 2-heptanone or n-butyl acetate.

  Developer is typically applied to the substrate by spin coating. Development time is a period effective to remove unexposed areas of the photoresist, with a typical time of 5-30 seconds. Development is typically carried out at room temperature. The development process can be performed without the use of a cleaning solution after development. In this regard, it has been found that the development process can result in a wafer surface that is free of residues and can eliminate such extra cleaning steps.

  The BARC layer, if present, is selectively etched using the resist pattern as an etch mask to expose the underlying hard mask layer. The hard mask layer is then selectively etched using the resist pattern as an etch mask as well, resulting in a patterned BARC layer and a hard mask layer. Suitable etching techniques and chemicals for etching the BARC and hard mask layers are known in the art and depend, for example, on the specific materials of these layers. A dry etching process such as reactive ion etching is typical. The resist pattern and patterned BARC layer are then removed from the substrate using known techniques, such as oxygen plasma ashing.

  The following non-limiting examples are illustrative of the invention.

Examples 1 to 5: Synthesis of Monomers 1 to 5 Synthesis of monomer 1

  2,2-Difluorohexanoic acid (50 g) was dissolved in 250 mL of methylene chloride in a round bottom flask at 0 ° C. under a nitrogen atmosphere. Oxalyl chloride (27.6 mL) was added dropwise and 1 to a few drops of dimethylformamide were added. The reaction mixture was slowly warmed to room temperature and allowed to stir at this temperature for 4 hours. No further inspection steps were performed before the next step.

  2,3-dihydroxypropyl methacrylate (22.43 g) was dissolved in 100 mL and this solution was added to the reaction mixture at 0 ° C., followed by the slow addition of pyridine (56.4 mL). The reaction mixture was slowly warmed to room temperature and allowed to stir at this temperature for 16 hours.

  The reaction mixture is transferred to 200 mL of deionized water, the organic phase is washed successively with 1N HCl and aqueous sodium bicarbonate, and deionized water, and the collected organic solution is dried over sodium sulfate, filtered, and vacuumed Concentration gave the monomer 1 shown above.

  Example 2: Synthesis of monomer 2

1,1,1-Tris (hydroxymethyl) ethane (23 g, 191 mmol) and triethylamine (26.7 mL, 191 mmol) were dissolved in 100 mL dimethylformamide in a round bottom flask under a nitrogen atmosphere. Methacryloyl chloride (9.3 mL, 96 mol) was added dropwise at 0 ° C. The reaction mixture was slowly warmed to room temperature and allowed to stir at this temperature for 3 hours. The reaction mixture was transferred to 100 mL deionized water, extracted with ethyl acetate, and the organic phase was washed successively with aqueous NH ₄ Cl and deionized water. The collected organic solution was dried over sodium sulfate, filtered and concentrated in vacuo. Difluorohexanoic acid (14.23 g, 94 mmol) was added to the round bottom flask under a nitrogen atmosphere. DCM (100 mL) was added as a solvent and then DMF (0.2 mL) was injected. Oxalyl chloride (8 mL, 94 mmol) was added dropwise. The solution was stirred at room temperature until gas evolution ceased. 2,2-bis (hydroxymethyl) propyl methacrylate (8.00 g, 43 mmol) was dissolved in DCM (40 mL) and pyridine (17.1 mL, 213 mmol) and the solution was transferred to a dropping funnel. The solution was added dropwise at 0 ° C. The reaction mixture was slowly warmed to room temperature and allowed to stir at this temperature for 3 hours. The reaction mixture was then transferred to 100 mL deionized water and the organic layer was then washed with 1N HCl and brine. The solution was dried over sodium sulfate, filtered and concentrated in vacuo to give monomer 2 shown above.

  Example 3: Synthesis of monomer 3

1,1,1-Tris (hydroxymethyl) propane (25.67 g, 191 mmol) and triethylamine (26.7 mL, 191 mmol) were dissolved in 100 mL of dimethylformamide in a round bottom flask under a nitrogen atmosphere. Methacryloyl chloride (9.3 mL, 96 mol) was added dropwise at 0 ° C. The reaction mixture was slowly warmed to room temperature and allowed to stir at this temperature for 3 hours. The reaction mixture was then transferred to 100 mL of deionized water and extracted with ethyl acetate, and the organic phase was washed successively with aqueous NH ₄ Cl and deionized water. The collected organic solution was dried over sodium sulfate, filtered and concentrated in vacuo. Difluorohexanoic acid (14.23 g, 94 mmol) was added to the round bottom flask under a nitrogen atmosphere. DCM (100 mL) was added as a solvent and then DMF (0.2 mL) was injected. Oxalyl chloride (8 mL, 94 mmol) was added dropwise. The solution was stirred at room temperature until gas evolution ceased. 2,2-bis (hydroxymethyl) butyl methacrylate (8.6 g, 43 mmol) was dissolved in dichloromethane (40 mL) and pyridine (17.1 mL, 213 mmol) and the solution was transferred to a dropping funnel. The solution was added dropwise at 0 ° C. The reaction mixture was slowly warmed to room temperature and allowed to stir at this temperature for 3 hours. The reaction mixture was then transferred to 100 mL deionized water and the organic layer was then washed with 1N HCl and brine. The solution was dried over sodium sulfate, filtered and concentrated in vacuo to give monomer 3 shown above.

Example 4: Synthesis of monomer 4 Part A: Synthesis of monomer precursor

Prepare a cold solution of (Z) -but-2-ene-1,4-diol (50 g, 567.47 mmol) in CH ₃ CN (650 mL) to m-chloroperbenzoic acid (144 g, 584.49 mmol). Added. The mixture was stirred at 0 ° C. to room temperature for 24 hours. The formed benzoic acid was removed by filtration and the filtrate was washed with diethyl ether to remove unreacted m-chloroperbenzoic acid and remaining chlorobenzoic acid. The product was separated from the solution with diethyl ether to give 51.5 g (85%). Oxirane-2,3-diyldimethanol (5 g, 48.02 mmol), methacrylic acid (8.68 g, 100.84 mmol), tri-ethylamine (0.7 mL, 0.4.80 mmol), BHT (catalytic amount). , Added to CH ₃ CN in RBF fitted with a condenser. The reaction mixture was stirred at 50 ° C. for 48 hours. After the reaction mixture evaporated under reduced pressure, it was washed with diethyl ether to remove the remaining methacrylic acid. The product 1,3,4-trihydroxybutan-2-yl methacrylate was obtained.

  Part B: Synthesis of monomer 4

Oxacyl chloride (0.5 mL, 5.80 mmol) and a catalytic amount of DMF were added to a solution of 2,2-difluoropropionic acid (0.58 g, 5.27 mmol) in dry THF (6 mL). . The mixture was stirred at 0 ° C. for 2 hours. After a solution of 1,3,4-trihydroxybutan-2-yl methacrylate (0.25 g, 1.39 mmol), pyridine (0.53 mL, 6.59 mmol) in dry THF (5 mL) was added in THF. To the solution of 2-difluoropropanoyl chloride. The mixture was stirred for 16 hours until warm. The reaction mixture was cooled to 0 ° C. and then quenched with water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with 1N HCl solution and brine, filtered through Na ₂ SO ₄ and evaporated under reduced pressure. The crude product was purified to give monomer 4 shown above.

  Example 5: Synthesis of monomer 5

Oxacrylyl chloride (21.8 mL, 254.5 mmol) and a catalytic amount of DMF were added to a solution of 2,2-difluorohexanoic acid (35.26 g, 231.3 mmol) in dry MC (100 mL). . The mixture was stirred at 0 ° C. for 2 hours. After a solution of 1,3,4-trihydroxybutan-2-yl methacrylate (11 g, 27.8 mmol), pyridine (23.3 mL, 289.2 mmol) in dry MC (40 mL) was added to 2,2- Added to a solution of difluorohexanoyl chloride. The mixture was stirred for 16 hours until warm. The reaction mixture was cooled to 0 ° C. and then quenched with water. The layers were separated and the aqueous layer was extracted with MC. The organic layers were combined, washed with 1N HCl solution and brine, filtered through Na ₂ SO ₄ and evaporated under reduced pressure. The crude product was purified to obtain the ester compound monomer 5 shown above.

  Example 6: Synthesis of monomer 6

Prepare a solution of 1,3,4-trihydroxybutan-2-yl methacrylate (0.21 g, 1.10 mmol), pyridine (0.53 mL, 6.65 mmol) in dry THF (5 mL) at 0 ° C. , Acetyl chloride (0.4 mL, 5.54). The mixture was stirred for 16 hours until warm. The reaction mixture was cooled to 0 ° C. and then quenched with water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with 1N HCl solution and brine, filtered through Na ₂ SO ₄ and evaporated under reduced pressure. The crude product was purified to obtain the ester compound monomer 6 shown above.

Examples 7-12: Synthesis of Polymers 1-7 Example 7: Synthesis of Polymer 2

  13.16 g synthetic monomer, 0.84 g TBPMA monomer, and 7.0 g PGMEA were added to the glass bottle. The bottle was lightly shaken to mix its contents, then the bottle was placed in an ice bath to reach temperature equilibrium with the ice bath. 0.29 g initiator (vazo 67, white powder) was added to the reaction bottle and placed in an ice bath. 7.0 g of PGMEA was charged into a 100 mL three-necked round bottom equipped with a condenser. A thermocouple was allowed to reach the reaction mixture in order to measure and control the solvent reaction temperature throughout the polymerization. After the feed solution was delivered through the feed inlet, the reactor was heated to 97 ° C. ± 2 ° C. Once the reaction temperature of the reaction mixture reached the set temperature (97 ° C.), the feed solution was fed into the reactor at a feed rate of 250 μL over 13 seconds for a total feed time of up to 75 minutes. After feeding, the reactor was maintained at 97 ° C. for an additional 2 hours and the reaction mixture was cooled to room temperature with stirring. The average molecular weight and polydispersity of polymer 2 (shown above) were 14.7 K and 1.80, respectively.

Example 8: Synthesis of Polymer 3 To synthesize Polymer 3 with Monomer 1, the procedure of Example 7 was repeated except that the amount of initiator was 0.31 g. The average molecular weight and polydispersity of polymer 3 were 8.2K and 1.63, respectively. Thus, polymer 3 has the same structure as polymer 2 shown in Example 7 above, except for differences in molecular weight and polydispersity.

Example 9: Synthesis of Polymer 4 To synthesize Polymer 4 with Monomer 1, the procedure of Example 7 was repeated except that the amount of initiator was 0.32 g. The average molecular weight and polydispersity of polymer 4 were selectively 5.4K and 1.46. Thus, polymer 4 has the same structure as polymer 2 shown in Example 7 above, except for the differences in molecular weight and polydispersity.

Example 10: Synthesis of Polymer 5 The procedure of Example 7 was repeated except that monomer 1 was replaced by monomer 2 of Example 2 to synthesize polymer 5. The average molecular weight and polydispersity of polymer 5 were 10.6 K and 1.76, respectively.

Example 10: Synthesis of Polymer 6 The procedure of Example 7 was repeated except that monomer 1 was replaced with monomer 3 of Example 3 to synthesize polymer 6. The average molecular weight and polydispersity of polymer 6 were 10.0K and 1.61, respectively.

Example 11 Synthesis of Polymer 7 The procedure of Example 7 was repeated except that monomer 1 was replaced with monomer 5 of Example 5 to synthesize polymer 7. The average molecular weight and polydispersity of polymer 7 were selectively 7.0K and 1.44.

  Example 12: Synthesis of reference polymer 1:

  Polymer 1 shown in the above scheme was prepared by the general procedure of Example 7 above.

Example 13: Water Contact Angle Analysis The water contact angle (WCA) was evaluated for the polymer spin coating layers specified in Table 1 below. In Table 1, polymers 1-7 correspond to the polymers of the same names in Examples 7-12 above. Burnett et al. , J .; Vac. Sci. Techn. B, 23 (6), pages 2721-2727 (November / December 2005), in general, several water contact angles were evaluated: static, receding, advancing, sliding, and tilting. The results set forth in Table 1 below show that both the polymer and photoresist composition of the present invention are 64, 65, 66, 67, 68, 69, 70, 71 for both the polymer and the photoresist composition. , 72, 0, or a receding water contact angle greater than 75, and / or a sliding water contact angle of less than 20 degrees, which can be adjusted to achieve the desired water angle as desired by the device manufacturer. Show.

Examples 14 and 15: Preparation of photoresist composition Example 14: Preparation of photoresist A

  Methyl adamantyl methyl acrylate / α-gamma butyrolactone / hydroxy adamantyl methyl acrylate (corresponding weight ratio of corresponding repeating unit 40/30/20: methyl adamantyl methyl acrylate / α-gamma butyrolactone / hydroxy adamantyl methyl acrylate)

  2.338 g of methyladamantyl methyl acrylate / α-gamma butyrolactone / hydroxyadamantyl methyl acrylate (about 9,0000 weight average molecular weight, polymer structure shown above), 0.343 g of photoacid in a 250 mL polypropylene (PP) bottle Generators triphenylsulfonium perfluorobutylsulfonate, 0.035 g trioctylamine, 0.353 g polymer 1 (23.8 wt% in PGMEA), 48.331 g PGMEA, and 48.600 g methyl-2-hydroxyiso A photoresist composition (designated herein as Photoresist A) was prepared by mixing butyrate (methyl-2-hydroxyiosbutyrate) (HBM). The PP bottle was shaken at room temperature for 6 hours.

Example 15: Preparation of Photoresist B 2.338 g of methyladamantyl methyl acrylate / α-gamma butyrolactone / hydroxyadamantyl methyl acrylate (about 9,0000 weight average molecular weight, as indicated above in Example 14) in a 250 mL PP bottle Polymer structure), 0.343 g TPS-PFBuS, 0.035 g trioctylamine, 0.175 g polymer 2 (48.1 wt% in PGMEA), 48.509 g PGMEA, and 48.600 g HBM A photoresist composition (designated herein as photoresist B) was prepared. The PP bottle was shaken at room temperature for 6 hours.

Example 16 Lithography-Photoresist A
A 300 mm HMDS primed silicon wafer was spin coated with AR ™ 26N (Rohm and Haas Electronic Materials) to form a first bottom anti-reflective coating (BARC) on TEL CLEAN TRAC LITHIUS i +, 205 ° C. Followed by a 60 second baking process.

  The photoresist composition of Example 14 (Photoresist B) is spin coated over the BARC layer. The so-applied photoresist layer is then soft baked and imaged in an immersion lithography system with patterned radiation having a wavelength of 193 nm and an image focus of -012. Other imaging parameters are listed in Table 2 below. The exposed wafer is post-exposure baked at 90 ° C. for 60 seconds and then developed using tetraTMAH developer for about 30 seconds to obtain a well-resolved line / space photoresist relief image. The results are shown in Table 2 below after Example 14.

Example 17: Lithography-Photoresist B
A 300 mm HMDS primed silicon wafer was spin coated with AR ™ 26N (Rohm and Haas Electronic Materials) to form a first bottom anti-reflective coating (BARC) on TEL CLEAN TRAC LITHIUS i +, 205 ° C. Followed by a 60 second baking process.

  The photoresist composition of Example 15 (Photoresist B) is spin coated over the BARC layer. The so-applied photoresist layer is then soft baked and imaged in an immersion lithography system with patterned radiation having a wavelength of 193 nm and an image focus of -012. Other imaging parameters are listed in Table 2 below. The exposed wafer is post-exposure baked at 90 ° C. for 60 seconds and then developed using TMAH developer for about 30 seconds to obtain a well resolved line / space photoresist relief image. The results are as described in Table 2 below.

  In Table 2, exposure latitude (EL) is defined as the difference in exposure energy to print +/− 10% of the target diameter normalized by sizing energy. Line width fluctuation (LWR) is the deviation in line width measured over a given length. LWR is quantified as a 3σ deviation in width.

Claims (15)

A polymer comprising the structure of formula (I):
Where
X and X ′ are the same or different linkers;
R is hydrogen or a non-hydrogen substituent,
A and B are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent,
The polymer, wherein at least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen. The polymer has the structure of the following formula (IIA):
In formula (IIA),
X and X ′ are the same or different linkers;
R is hydrogen or a non-hydrogen substituent,
A and B are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent;
The polymer of claim 1, wherein at least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen.   The polymer of claim 1, wherein R ′ and R ″ are each independently hydrogen, fluorine, halogenated alkyl, non-halogenated alkyl, or heteroalkyl.   The polymer of claim 1, wherein X and X ′ are different.   The polymer of claim 1, wherein X and X ′ are the same. The polymer of claim 1, wherein at least one of X and X ′ is —CH ₂ —. Including the structure of the following formula (IIB):
In formula (IIB),
X, X ′, and X ″ are each the same or different linkers;
A, B, and C are each independently hydrogen or fluorine;
The polymer of claim 1, wherein R ′, R ″, and R ′ ″ are each independently hydrogen or a non-hydrogen substituent.   The polymer of claim 1, wherein the polymer comprises acrylate units. Said polymer comprises units obtained by polymerization of one or more monomers of the following formula (III):
In formula (III),
Y is hydrogen or optionally substituted alkyl;
X and X ′ are the same or different linkers;
R is hydrogen or a non-hydrogen substituent,
A and B are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent;
The polymer of claim 1, wherein at least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen.   The polymer of claim 1, wherein at least one of A and B is fluorine.   A photoresist composition comprising a photoactive component and the polymer of claim 1.   The photoresist composition of claim 10 further comprising a second different polymer. A method of processing a photoresist composition comprising:
Applying a layer of the photoresist composition of claim 10 on a substrate;
Exposing the photoresist composition layer to activating radiation;
Developing the exposed photoresist composition to provide a photoresist relief image.   The method of claim 12, wherein the photoresist composition layer is immersion exposed. A monomer comprising the structure of formula (I):
Where
X and X ′ are the same or different linkers,
R is hydrogen or a non-hydrogen substituent,
A and B are each independently hydrogen or fluorine,
R ′ and R ″ are each independently hydrogen or a non-hydrogen substituent;
A monomer wherein at least one of R ′ and R ″ is a halogen or a non-hydrogen substituent other than a halogen substituent when R is hydrogen.